CN109422282A - A kind of method of synthesizing alkanes catalyst for hydroisomerizing carrier - Google Patents
A kind of method of synthesizing alkanes catalyst for hydroisomerizing carrier Download PDFInfo
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
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- C07—ORGANIC CHEMISTRY
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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2767—Changing the number of side-chains
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Abstract
A kind of method that the present invention discloses molding MgAPO-11 molecular sieve of the directly synthesis with intended shape, the molded molecular sieve are used directly as alkane hydroisomerization catalyst carrier, are related to technical field of molecular sieve preparation.Its main feature are as follows: silicon source, phosphorus source, magnesium source, Fluorine source, organic amine, ionic liquid and water are mixed in a certain ratio obtained gel, then by gained gel by intended shape processing molding, the formed body being made of completely MgAPO-11 molecular sieve can be obtained in formed gel crystallization under certain condition.Molded molecular sieve is made in a step of the invention, uses directly as catalyst carrier, simplifies catalyst preparation process.It is compared with the traditional method, this method preparation process is simple, and raw material availability is high, and waste liquid discharging amount is low, has broad application prospects.
Description
Technical field
The present invention relates to a kind of method of synthesizing alkanes catalyst for hydroisomerizing carrier, concretely relate to by
The preforming synthetic method for the alkane hydroisomerization catalyst carrier that MgAPO-11 molecular sieve is constituted.
Background technique
In recent years, with the continuous growth of global economy, market requires increasingly gasoline, diesel oil and quality of lubrication oil
It is high.In order to improve the quality of oil product, n-alkane therein must remove as much as possible.For gasoline, octane number is to measure it
One important quantizating index of quality, high-octane gasoline is more high-efficient than the gasoline combustion of low octane rating, and same carbon number
The octane number of isoparaffin be generally higher than the octane number of n-alkane, be that isoparaffin can by normal alkane isomerization therefore
To improve the octane number of gasoline；For diesel oil, low temperature fluidity is one of the main standard for measuring its quality, if energy will just
Structure alkane selectivity is isomerized to isoparaffin, then its condensation point or cold filter plugging point can be reduced, so as to improve its cryogenic property.Just
For lubricating oil, the quality of quality and base oil performance has substantial connection, because content of the base oil in lubricating oil is usual
It is 70%~99%；Long-chain normal paraffin (also referred to as wax) pour point and condensation point in base oil is higher, and low temperature flow is poor, cannot
Meets the needs of present engine；The good lubricating oil of low temperature flow is obtained, the wax in base oil must just be removed.
The technique of n-alkane mainly has solvent dewaxing, catalytic dewaxing and isomerization dewaxing in industrial removing oil product at present.
Compared with first two technique, isomerization dewaxing technique is to make wax molecule that isomerization reaction occur, so that wax be made to be changed into ideal composition,
The technique has the advantages that product yield is high, high-quality.
By long-chain normal paraffin selectivity be isomerized to the few short chain isomerism alkane of side chain can effectively improve diesel oil,
The low temperature flow of lubricating oil.Using phosphoric acid magnalium (MgAPO-11) molecular sieve with AEL structure as the catalyst of carrier, in length
Excellent performance is shown in chain n-alkane hydroisomerization reaction, is concerned in recent years.
Activity of Magnesium Aluminophosphate Molecular Sieve (MgAPO-11) has one-dimensional ten-ring straight hole structure, and aperture size is
The molecular sieve is to enter aluminium phosphate molecular sieve (AlPO by magnesium (Mg) same order elements aluminium (Al)4- 11) what skeleton was formed.Aluminum phosphate
Molecular sieve (AlPO4- 11) it is a kind of novel molecular sieve developed by U.S. combinating carbide company early 1980s, has
Good adsorptivity, thermal stability and hydrothermal stability, but since its skeleton structure is in electroneutral, do not have ion-exchange performance
Surface acidity is extremely weak, its application is made to be very limited.Replace the Al in aluminium phosphate molecular sieve skeleton to introduce skeleton in magnesium, makes point
Sub- sieve skeleton frame takes negative electrical charge, if the cation of compensation skeleton negative electrical charge is H+, just will form on MgAPO-11 molecular sieve
With strong acidityTherefore acidic site Mg-OH-P ol group is provided with surface acidity.Based on MgAPO-11
The catalyst of molecular sieve shows excellent catalytic performance in long-chain normal paraffin hydroisomerization reaction.In recent years, with
The market demand of the fast development of national economy, MgAPO-11 molecular sieve is gradually increased.MgAPO-11 molecular sieve is as catalysis
When agent practical application in industry, the finished granule that specific shape and size is made is generally required.It includes molecule that finished product, which prepares work process,
Sieve the synthesis of powder and the machine-shaping of catalyst granules.
Hydrothermal synthesis method is used in the compound probability of MgAPO-11 molecular sieve powder, this method takes water as a solvent, and material is pressed
Certain proportion is mixed to prepare colloidal sol, and colloidal sol between 80~200 DEG C and carries out crystallization under the self-generated pressure of water, and crystallization terminates
Afterwards, product is filtered, washed and is dried to obtain molecular sieve powder.Shaping of catalyst needs molecular sieve powder and binder, increases
The additives such as modeling agent, extrusion aid, pore creating material are mixed to get plastic body, then obtain by kneaded and formed, health, drying and roasting
Finished product.
Such as Yang Xiaomei et al. is by raw material in molar ratio 0.03MgO: 1.0Al2O3∶xP2O5∶1.2n-Pr2NH∶50H2O is made into
Then Primogel is fitted into the stainless steel cauldron with polytetrafluoroethyllining lining by Primogel, at 200 DEG C crystallization 4~
72h, obtained product are separated by filtration with after deionized water washing, dry at 110 DEG C, and roast at 560 DEG C to get arriving
MgAPO-11 powder (Chinese Journal of Catalysis, 2006,27:1039~1044).Patent CN1843625A
Disclose the catalyst and preparation method thereof for hydroisomerization reaction of alkane, this method molecular sieve powder and binder are made
Hole agent, extrusion aid, water etc. mix and send into clover bar shaped, and then drying, roasting obtain catalyst carrier.Pt is loaded
In on this carrier, finished catalyst is obtained by drying, roasting, which is used for n-dodecane hydrocarbon hydroisomerization reaction
In.
Boehmite (is converted into Al by patent CN103265396A2O3Content be 60.6%), Mg (CH3COO)2·
4H2O, the phosphoric acid, DPA (di-n-propylamine), deionized water that mass concentration is 85% press Al2O3:MgO:P2O5:DPA:H2O=
5.709:0.220:7.817:3.5:23.053 weight fraction ratio stir evenly gel is made after at 180 DEG C crystallization 48h, obtain
To product be separated by filtration with after deionized water washing, dried at 110 DEG C, MgAPO-11 point be made after roasting at 650 DEG C
Son sieve powder.By the MgAPO-11 molecular sieve powder compression molding after roasting, it is prepared into the particle having a size of 20~40 mesh, and pass through
Drying, roasting are crossed, catalyst is made, alkylation of the catalyst for naphthalene is prepared in the reaction of 2,6- dimethylnaphthalene.
Above method first prepares molecular sieve powder, and finished catalyst is made in reshaping, drying and roasting, and process flow is long,
Process is complicated.In addition, molecular sieve water heat crystallization process carries out under high pressure, there are security risks；Powder is filtered, washed process
A large amount of waste water are generated, environmental pollution is caused；Shaping of catalyst needs to be added the additives such as binder, due to the introducing of additive,
The content of molecular sieve is unable to reach 100% generally 60~80% in finished catalyst, influences molecular sieve performance performance.
In order to solve problem above, people, which are directed to, simplifies molecular sieve in molecular sieve catalyst preparation process and raising formed body
Content two in terms of done numerous studies.
Molecular sieve identical with raw material shape is directly made using having effigurate raw material in researchers, no longer needs into
Type can simplify molecular sieve catalyst preparation process.
Such as Sachse et al. is with SiO2Integral material is that raw material is prepared for molding ZSM-5 catalyst.This method is by SiO2It is whole
It is SiO that body material, which is placed in molar ratio,2:NaOH:NaAlO2:TPAOH:H2In the solution of O=1:0.15:0.09:0.004:33, in
Crystallization for 24 hours, obtains preformed catalyst (Micropor.Mesopor.Mater., 2011,140 (1-3): 58-68) at 150 DEG C.It should
Method uses SiO2Silicon source of the integral material as Zeolite synthesis, crystallization process keep solid phase, but silicon source NaAlO2Deng other raw materials
Still exist in aqueous solution, crystallization is still water-heat process.Although molecular sieve finished product maintains the shape of integral material, due to
Reaction raw materials are respectively in solid-liquid two-phase, and reaction process cannot be complete by mass transfer and limit, crystallization, and the content of ZSM-5 is only in finished product
38%.
FranziskaScheffler et al. is prepared for molding ZSM-5 catalyst by raw material of foamed aluminium integral material.It should
It is Na that foamed aluminium integral material is placed in molar ratio by method2O:TPABr:SiO2:H2The solution of O=0:423:0.055:1:72.4
In, crystallization for 24 hours, obtains preformed catalyst at 150 DEG C.The method uses foamed aluminium integral material for silicon source, other raw materials are also still
So in aqueous solution, the content of ZSM-5 also only has 13% (Micropor.Mesopor.Mater., 2004,67 (1): 53-9).
By part material, monolithic devices catalysis has been made in crystallization, a step to above method under hydrothermal conditions in the form of integral material
Agent simplifies preparation process.But other raw materials are still present in aqueous solution, crystallization is still water-heat process, and it is hidden to there is safety
Suffer from；Reaction raw materials point are in solid-liquid two-phase, and reaction process is contained the raw material not changed, molecular sieve in finished product by mass transfer and limit
Content is not high.In addition, these methods use integral material shape raw material, limited by raw material material, shape is single.And at present at
The practical finished form of type catalyst is abundant, includes spherical shape, bar shaped, cylinder, honeycombed, bunge bedstraw herb shape, cloverleaf pattern, external tooth
Wheel shape, non-porous external tooth wheel shape, it is quincunx, porous it is quincunx, seven apertures in the human head is spherical, non-porous spherical, seven muscle wheel shapes, four hole shapes, four leaves
Butterfly etc..
Nevertheless, preparing MgAPO-11 molecular sieve carrier by raw material of integral material, similar work there is no.
In order to improve the content of molecular sieve in molecular sieve catalyst finished product, researchers do a lot of work, and will form
The additives crystallization such as binder of Cheng Tianjia is molecular sieve.
Such as patent CN106745057A discloses a kind of preparation method of AEI/MFI eutectic molecular sieve catalyst.The party
Method is by after MFI type Si-Al molecular sieve, FAU type Si-Al molecular sieve and silica solution mixed-forming, further containing the water-soluble of organic amine
In liquid, hydrothermal treatment is converted into integrated AEI/MFI eutectic molecular sieve catalyst, using roasting obtain catalyst at
Product.
Patent CN101348260A discloses a kind of preparation method of MFI/FAU composite molecular sieve catalyst.This method will
After MFI crystal seed, FAU molecular sieve, silicon source and silicon source mixed-forming, further in the steam containing organic amine, using Dry gel conversion method
Legal system obtains integrated MFI/FAU composite molecular sieve catalyst, then crystallization roasting obtains finished catalyst.
Above method formed body obtained crystallization again after mixing molecular sieve powder with binder, is transformed into binder
Molecular sieve.Though the available formed body being made of completely molecular sieve of the method, there is still a need for synthesis of molecular sieve original powders；Forming process
Crystallization steps are increased, manufacturing cost is improved.
The present invention proposes a kind of preforming synthetic method of molecular sieve, can reach simultaneously simplified molecular sieve catalyst preparation process and
Improve the target of molecular sieve content in formed body.Catalyst based on MgAPO-11 molecular sieve is in long-chain normal paraffin hydro-isomerization
Change in reaction and show excellent catalytic performance, present invention is particularly directed to MgAPO-11 molecular sieves, provide a kind of preforming synthesis
Method.
Summary of the invention
Present invention aims at the process flow for simplifying molecular sieve catalyst preparation, directly preparation has the pure of intended shape
Molecular screen material provides a kind of preforming synthetic method of alkane hydroisomerization catalyst carrier.
The scheme that the present invention solves above-mentioned technical problem is as follows:
A kind of alkane hydroisomerization catalyst carrier is the AEL structure MgAPO-11 that there is International Zeolite Association to confirm
Molecular sieve, synthesis process are as follows: by synthesized gel rubber by the processing molding of desired shape processing, then direct crystallization obtains and formed gel
The consistent molded molecular sieve of shape, includes the following steps,
(1) silicon source, phosphorus source, magnesium source, Fluorine source, organic amine, ionic liquid and water are pressed into Al2O3:P2O5:MgO:F-: organic amine:
Ionic liquid: H2The mixing of O=1:0.2~5:0.002~6:0.01~8:0.01~9:0.005~5:2~100 molar ratio
Gel is made,
(2) gel made from step (1) is processed into the formed gel with required shape,
(3) formed gel made from step (2) is placed in closed container, at 100~270 DEG C crystallization 10min~
10d obtains the molded molecular sieve with AEL topological structure.
Magnesium source of the present invention is one or more of magnesium acetate, magnesium chloride, magnesium nitrate.
Silicon source of the present invention, phosphorus source, magnesium source, Fluorine source, organic amine, ionic liquid and water molar ratio be preferably
Al2O3:P2O5:MgO:F-: organic amine: ionic liquid: H2O=1:0.4~2.0:0.002~1:0.02~2.0:0.1~3.0:
0.01~3.0:25~60.
Organic amine of the present invention is the one or more of di-n-propylamine, diisopropylamine, N- methylimidazole.
The preparation of gel of the present invention uses this field routine operation method, for example in certain temperature and strong stirring bar
Under part, silicon source, phosphorus source, magnesium source, Fluorine source, organic amine, ionic liquid are added in deionized water mix according to a certain percentage, is obtained
It is uniformly mixed containing silicon source, phosphorus source, magnesium source, Fluorine source, organic amine and ionic liquid aqueous gel.
Gel forming of the present invention be this field routine operation, be for example extruded moulding, compression forming, oil column at
Type, rotational forming, spray shaping or granulating, the shape of obtained formed gel can be spherical shape, bar shaped, cylinder, honeycombed,
Bunge bedstraw herb shape, cloverleaf pattern, external tooth wheel shape, non-porous external tooth wheel shape, it is quincunx, porous it is quincunx, seven apertures in the human head is spherical, non-porous spherical,
Seven muscle wheel shapes, four hole shapes or four leaf butterfly shapes etc..The shape and size specifically used are selected according to actual service conditions requirement
It determines.Gel of the present invention can carry out the pretreatment of certain forms before forming operation, improve its plasticity, with guarantee at
The convenient operation of type process.Gel can be for example aged to 3~6h at normal temperature, then handled under the conditions of 50 DEG C~110 DEG C
5h~12h removes water a part of in gel, obtains the solid of shaping, then processing and forming.
It needs to add ionic liquid in gel synthesized by the present invention, one or more kinds of ionic liquids can be added
Body.The anion of added ionic liquid can be Br-、I-、Cl-、CH3COO-One or both of
More than；Cation is alkyl-substituted imidazol ion [Rim]+, alkyl-substituted pyridinium ion [Rpy]+, quaternary ammonium alkyl salt ion
[NR4]+One or more of, R is the alkyl containing 1 to 16 carbon.
Silicon source of the present invention is one of boehmite, activated alumina, aluminium hydroxide, aluminium isopropoxide or two
Kind or more.
Phosphorus source of the present invention be one or both of phosphoric acid, monoammonium phosphate, ammonium dihydrogen phosphate, triammonium phosphate with
On.
Fluorine source of the present invention is one or more of hydrofluoric acid, sodium fluoride, ammonium fluoride.
The preferred crystallization temperature of crystallization process of the present invention is 120~240 DEG C, and preferably crystallization time is 20min~7d.It is brilliant
Formed gel is placed in the pressure resistant vessel of this field routine and carries out by change process, and a certain amount of water can be pre-placed in container,
But it is not necessary to water is directly contacted with formed gel.Crystallization process uses the heating method of this field routine, for example, oil bath
Heating, baking oven heating and microwave heating.
Crystallization terminates, and mold compound obtained by the present invention is not necessarily to filtration washing.Crystallization product maintains formed gel phase
Same shape and size, are made of molecular sieve completely, and sample molecule sieve skeleton structure is International Zeolite Association in following embodiments
The AEL structure of confirmation.Crystallization product does powder x-ray diffraction after crushing, diffraction maximum position and relatively strong and weak as follows:
To help to understand the present invention, " preforming " term is defined below.The term of this definition has the present invention related
The normally understood meaning of the those of ordinary skill in field.
Unless otherwise stated, " preforming " refers in advance by gel used in synthesis of molecular sieve, by compressing, squeezing herein
The methods of out, rotate, is spraying, it is processed into the process or step of the formed gel with certain shapes, size and mechanical strength.
In conclusion the present invention provides a kind of preformation method of synthesizing alkanes catalyst for hydroisomerizing carrier, have
Following advantage:
One step is made molded molecular sieve and simplifies catalyst preparation process.Formed body is made of molecular sieve completely, is improved
The content of molecular sieve in per volume of catalyst, can be improved its catalytic activity.This method directly obtains molded molecular sieve, avoids
The filtration washing step of conventional molecular sieve production process, waste liquid discharging amount is low, environmental-friendly.
Detailed description of the invention
Fig. 1 is the XRD spectra of sample in the embodiment of the present invention 1.
Fig. 2 is the SEM figure of sample in cross section in the embodiment of the present invention 1.
Fig. 3 is the molding dry glue of the embodiment of the present invention 1 and the cylinder bar shaped MgAPO-11 molecular sieve of pre-shaping method synthesis
Photo in kind.
Specific embodiment
The following examples will be further described the present invention, but not thereby limiting the invention.
1 embodiment of the present invention of table, 1~5 synthesis condition.
Comparative example 1
Activity of Magnesium Aluminophosphate Molecular Sieve (MgAPO-11) is synthesized according to method provided by patent CN1843625A, and carries out positive ten
The evaluation of two hydroisomerization reaction of alkane.
By 16.2g boehmite (78.6wt%Al2O3) and 0.97g magnesium nitrate hexahydrate be placed in 103g water, stirring simultaneously
The phosphoric acid that 28.8g concentration is 85wt% is added dropwise, stirs evenly simultaneously aging 10 hours；15.3g di-n-propylamine is added, stirs evenly,
Gel is made, places it in the crystallizing kettle with polytetrafluoroethylkettle kettle lining, closed crystallization 60 hours at 190 DEG C, takes out, it is cold
But, it filters, 110 DEG C of drying obtain molecular screen primary powder.The original powder is taken to do XRD analysis, which is MgAPO-11.
The MgAPO-11 molecular sieve for taking the above-mentioned preparation of 180g is uniformly mixed with 100gSB powder, 15g sesbania powder.Measure 110g
Concentration is that the nitric acid of 10wt% and 110 milliliters of water are added above-mentioned mixed-powder after mixing, after abundant kneading on banded extruder
Cylinder bar shaped is squeezed out, is then dried at 110 DEG C 24 hours, 600 DEG C roast 24 hours, obtain shaping of catalyst carrier.
Above-mentioned shaping carrier 10g is taken, 20~40 mesh are crushed to, using the dipping method of common pack hole by 3.76ml
H2PtCl solution (every ml 0.0133g containing Pt) impregnates 16 hours, then dries at 120 DEG C 4 hours, 480 DEG C prepare for roasting 8 hours
At the catalyst containing 0.5wt%Pt.
It takes 100mL catalyst to be fitted into stainless steel tube reactor, is evaluated with n-dodecane hydrocarbon hydroisomerization reaction.
Reaction condition are as follows: reaction pressure 0.1MPa, n-dodecane hydrocarbon liquid air speed are 1.0h-1, mole of hydrogen and n-dodecane hydrocarbon
Than being 15, reaction product has online gas chromatographic analysis, is as a result listed in table 2.
2 n-dodecane of table hydroisomerization reaction result on the catalyst of 0.5wt%Pt/MgAPO-11
The amount of the unconverted positive structure dodecane hydrocarbon of positive structure dodecane hydrocarbon conversion rate (%)=1-/positive structure dodecane hydrocarbon charging amount
× 100%
The positive structure dodecane hydrocarbon of amount/all conversions of isomerisation selectivity (%)=be converted into isomerization (branch) dodecane
Total amount × 100%
Isomerization yield (%)=isomerisation selectivity (%) × positive structure dodecane hydrocarbon conversion rate (%) × 100%
Embodiment 1
By 17.35g boehmite (78.6wt%Al2O3) be placed in 250ml beaker, 95.39g deionized water, room is added
It is stirred 30 minutes under the conditions of temperature；The phosphoric acid that 33.90g concentration is 85wt% is added, stirs 3 hours；1.72g magnesium acetate is added, stirs
It mixes 30 minutes；The hydrofluoric acid that 1.34g concentration is 40wt% is added, stirring 30 minutes is continued；8.12g di-n-propylamine is added,
Stirring 30 minutes；It is eventually adding 28.09g 1- ethyl -3- methy limidazolium ionic liquid.Said mixture is stirred evenly
Then gelled is toasted 30 minutes under the conditions of 90 DEG C.The plasticity gel mixture that aforesaid operations are obtained is using double spiral shells
Bar banded extruder is extruded into the cylinder bar shaped of diameter 2mm.Obtained forming cylinder bar shaped gel is placed in polytetrafluoroethylkettle kettle
In the crystallizing kettle of lining, closed crystallization 3 days at 210 DEG C.
Crystallizing kettle is cooled to room temperature after crystallization, obtains the cylindrical bars shape molded molecular sieve of diameter about 2mm.It will molding
Molecular sieve grind into powder does XRD analysis, which is MgAPO-11, as shown in Figure 1.Electromicroscopic photograph shows that formed body is complete
It is made of the molecular sieve crystal of intergrowth, and contains macropore, as shown in Figure 2.Molded molecular sieve maintains the shape of formed gel
Shape, as shown in Figure 3.
Above-mentioned molding MgAPO-11 molecular sieve 2g is taken, 20~40 mesh is crushed to, takes 0.27mL H2PtCl6(every mL contains solution
Pt 0.037g) with 1.73mL deionized water be mixed and made into solution, using common pack hole dipping method impregnate 12h, and in
Room temperature is dried under vacuum condition, at 400 DEG C, H24h is restored under atmosphere (25ml/min), is prepared into 0.5wt%Pt/MgAPO-11
Catalyst.
It takes 100mL catalyst to be fitted into stainless steel tube reactor, is evaluated with n-dodecane hydrocarbon hydroisomerization reaction.
Reaction condition are as follows: reaction pressure 0.1MPa, n-dodecane hydrocarbon liquid air speed are 1.0h-1, mole of hydrogen and n-dodecane hydrocarbon
Than being 15, reaction product has online gas chromatographic analysis, is as a result listed in table 3.Within the scope of 260-320 DEG C, this patent preparation
0.5wt%Pt/MgAPO-11 catalyst has high n-dodecane hydrocarbon conversion rate, isomerisation selectivity and isomerization yield.
3 n-dodecane of table hydroisomerization reaction result on the catalyst of 0.5wt%Pt/MgAPO-11
Compared with the method provided by the patent CN1843625A, this patent is using the molding MgAPO-11 synthesized as carrier, system
The method of standby molecular sieve carrier is more simple.Synthesized carrier molecule sieve content is high, and catalyst has more excellent catalysis
Performance.
Embodiment 2
By 17.35g boehmite (78.6wt%Al2O3) be placed in 250ml beaker, 129.23g deionized water is added,
It stirs 30 minutes under room temperature；The phosphoric acid that 53.08g concentration is 85wt% and the biphosphate that 6.152g purity is 99% is added
Ammonium stirs 3 hours；0.025g magnesium chloride is added, stirs 30 minutes；The hydrofluoric acid that 0.14g concentration is 40wt% is added, is continued
Stirring 30 minutes；32.46g di-n-propylamine and 6.58g N- methylimidazole (1-mim) are added, is stirred 30 minutes；It is eventually adding
0.31g N- butyl-pyridinium acetate ionic liquid.Said mixture is stirred evenly into gelled, then under the conditions of 110 DEG C
Baking 30 minutes.The plasticity gel mixture that aforesaid operations are obtained uses double screw banded extruder, is extruded into clover bar shaped.It will
Obtained molding clover bar shaped gel is placed in the crystallizing kettle with polytetrafluoroethylkettle kettle lining, the closed crystallization 7 at 240 DEG C
It.
Crystallizing kettle is cooled to room temperature after crystallization, obtains clover bar shaped molded molecular sieve.Molded molecular sieve is ground
It clays into power and does XRD analysis, which is MgAPO-11.
Embodiment 3
By 17.35g boehmite (78.6wt%Al2O3) be placed in 250ml beaker, 44.23g deionized water, room is added
It is stirred 30 minutes under the conditions of temperature；The phosphoric acid that 12.33g concentration is 85wt% is added, stirs 3 hours；34.27g magnesium nitrate is added, stirs
It mixes 30 minutes；The hydrofluoric acid that 12.03g concentration is 40wt% and the ammonium fluoride that 1.00g purity is 99% are added, stirring 30 is continued
Minute；1.35g di-n-propylamine is added, is stirred 30 minutes；It is eventually adding 45.31g 1- butyl -3- methylimidazole tetrafluoro boric acid
Ionic liquid and 38.31g 1- ethyl -3- methy limidazolium ionic liquid.Said mixture is stirred into gel
Then shape toasts 30 minutes under the conditions of 75 DEG C.The plasticity gel mixture roller forming that aforesaid operations are obtained.By gained
To molding spherical gel be placed in polytetrafluoroethylkettle kettle lining crystallizing kettle in, closed crystallization 20 minutes at 240 DEG C.
Crystallizing kettle is cooled to room temperature after crystallization, obtains spherical molded molecular sieve.Molded molecular sieve is pulverized
XRD analysis is done at end, which is MgAPO-11.
Embodiment 4
By 17.35g boehmite (78.6wt%Al2O3) be placed in 250ml beaker, 32.03g deionized water, room is added
It is stirred 30 minutes under the conditions of temperature；The phosphoric acid that 12.33g concentration is 85wt% is added, stirs 3 hours；0.06g magnesium acetate is added, stirs
It mixes 30 minutes；The hydrofluoric acid that 13.37g concentration is 40wt% is added, stirring 30 minutes is continued；Add 32.46g di-n-propylamine
With 8.11 diisopropylamines, stir 30 minutes；It is eventually adding 0.22g etamon chloride ionic liquid.Said mixture is stirred
Then uniform gelled is toasted 30 minutes under the conditions of 90 DEG C.The plasticity gel mixture that aforesaid operations are obtained uses
Single-screw extruder is extruded into honeycombed.Obtained formed honeycomb shape gel is placed in the crystallization with polytetrafluoroethylkettle kettle lining
In kettle, closed crystallization 20 minutes at 240 DEG C.
Crystallizing kettle is cooled to room temperature after crystallization, obtains honeycombed molded molecular sieve.Molded molecular sieve is ground into
Powder does XRD analysis, which is MgAPO-11.
Embodiment 5
By 14.74g boehmite (78.6wt%Al2O3) and 4.09g purity be 99% aluminium isopropoxide be placed in 250ml
In beaker, 103.37g deionized water is added, stirs 30 minutes under room temperature；The phosphoric acid that 12.33g concentration is 85wt% is added,
Stirring 3 hours；0.06g magnesium acetate is added, stirs 30 minutes；The hydrofluoric acid that 0.14g concentration is 40wt% is added, continues to stir
30 minutes；1.35g di-n-propylamine is added, is stirred 30 minutes；It is eventually adding 0.14g nitric acid second ammonium ion liquid.It will be above-mentioned mixed
It closes object and stirs evenly gelled, then toasted 30 minutes under the conditions of 110 DEG C.The plasticity gel that aforesaid operations obtain is mixed
It closes object and spheric granules is prepared into using oil-drop method.Obtained shaped granule shape gel is placed in polytetrafluoroethylkettle kettle
In the crystallizing kettle of lining, closed crystallization 7 days at 120 DEG C.
Crystallizing kettle is cooled to room temperature after crystallization, obtains graininess molded molecular sieve.Molded molecular sieve is ground into
Powder does XRD analysis, which is MgAPO-11.
Table 2 is the XRD diffraction maximum position of sample and relatively strong and weak in the embodiment of the present invention 1~5.
As seen from the above table, the MgAPO-11 molecule of pure phase can be prepared in the Reaction conditions range that this method is stated
Sieve.
Claims (10)
1. a kind of method of synthesizing alkanes catalyst for hydroisomerizing carrier, carrier is the AEL that there is International Zeolite Association to confirm
Structure MgAPO-11 molecular sieve, it is characterised in that: by synthesized gel rubber by it is expected shape processing processing molding, then crystallization obtain and at
The consistent molded molecular sieve of type gel shape, includes the following steps,
(1) silicon source, phosphorus source, magnesium source, Fluorine source, organic amine, ionic liquid and water are pressed into Al2O3:P2O5:MgO:F-: organic amine: ion
Liquid: H2O=1:0.2~5:0.002~6:0.01~8:0.01~9:0.005~5:2~100 molar ratio is mixed to prepare
Gel,
(2) gel made from step (1) is processed into the formed gel with required shape,
(3) formed gel made from step (2) is placed in closed container, crystallization 10min~10d, obtains at 100~270 DEG C
To the molded molecular sieve with AEL topological structure.
2. according to the method described in claim 1, it is characterized by: magnesium source be one of magnesium acetate, magnesium chloride, magnesium nitrate or
It is two or more.
3. according to the method described in claim 1, it is characterized by: silicon source, phosphorus source, magnesium source, Fluorine source, organic amine, ionic liquid
Molar ratio with water is Al2O3:P2O5:MgO:F-: organic amine: ionic liquid: H2O=1:0.4~2.0:0.002~1:0.02~
2.0:0.1~3.0:0.01~3.0:25~60.
4. according to the method described in claim 1, it is characterized by: organic amine is di-n-propylamine, diisopropylamine, N- methylimidazole
One or more of.
5. directly brilliant according to the method described in claim 1, it is characterized by: synthesized gel rubber is pre-processed into intended shape
Change a step and the formed body being made of molecular sieve is made.
6. added according to the method described in claim 1, it is characterized by: need to add ionic liquid in synthesized gel rubber
The anion of ionic liquid is Br-、I-、Cl-、CH3COO-One or more of；Cation is alkyl
Substituted imidazol ion [Rim]+, alkyl-substituted pyridinium ion [Rpy]+, quaternary ammonium alkyl salt ion [NR4]+One of or two
Kind or more, R is the alkyl of C1-C16.
7. according to claim 1 with the method, it is characterised in that: silicon source be boehmite, activated alumina, hydroxide
One or more of aluminium, aluminium isopropoxide.
8. according to claim 1 with the method, it is characterised in that: phosphorus source be phosphoric acid, monoammonium phosphate, ammonium dihydrogen phosphate,
One or more of triammonium phosphate.
9. according to the method described in claim 1, it is characterized by: Fluorine source be one of hydrofluoric acid, ammonium fluoride, sodium fluoride or
It is two or more.
10. according to the method described in claim 1, it is characterized by: the crystallization temperature of the crystallization process be 120~240 DEG C,
Crystallization time is 20min~7d.
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